US5942580A - Acrylic rubber composition - Google Patents
Acrylic rubber composition Download PDFInfo
- Publication number
- US5942580A US5942580A US08/610,948 US61094896A US5942580A US 5942580 A US5942580 A US 5942580A US 61094896 A US61094896 A US 61094896A US 5942580 A US5942580 A US 5942580A
- Authority
- US
- United States
- Prior art keywords
- acrylic rubber
- group
- rubber composition
- none none
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 229920000800 acrylic rubber Polymers 0.000 title claims abstract description 60
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 60
- -1 alkyl vinyl ethers Chemical class 0.000 claims abstract description 75
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 31
- 150000002367 halogens Chemical class 0.000 claims abstract description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000000596 cyclohexenyl group Chemical class C1(=CCCCC1)* 0.000 claims description 5
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 2
- XGDAKJKCJURQAF-UHFFFAOYSA-N azane;carbamic acid Chemical compound N.N.NC(O)=O XGDAKJKCJURQAF-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 65
- 238000007906 compression Methods 0.000 abstract description 45
- 230000006835 compression Effects 0.000 abstract description 45
- 230000032683 aging Effects 0.000 abstract description 33
- 239000004711 α-olefin Substances 0.000 abstract description 21
- 230000000704 physical effect Effects 0.000 abstract description 18
- 206010040880 Skin irritation Diseases 0.000 abstract description 15
- 230000036556 skin irritation Effects 0.000 abstract description 15
- 231100000475 skin irritation Toxicity 0.000 abstract description 15
- 230000006866 deterioration Effects 0.000 abstract description 13
- 239000000047 product Substances 0.000 description 43
- 229920000642 polymer Polymers 0.000 description 22
- 238000004898 kneading Methods 0.000 description 13
- 238000009472 formulation Methods 0.000 description 12
- 125000005396 acrylic acid ester group Chemical group 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 6
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 229940114930 potassium stearate Drugs 0.000 description 4
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001935 cyclohexenes Chemical class 0.000 description 3
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 3
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- OOKDYUQHMDBHMB-UHFFFAOYSA-N 3,6-dichloro-2-methoxybenzoic acid;2-(2,4-dichlorophenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CNC.COC1=C(Cl)C=CC(Cl)=C1C(O)=O.OC(=O)COC1=CC=C(Cl)C=C1Cl OOKDYUQHMDBHMB-UHFFFAOYSA-N 0.000 description 2
- ADPYSZNUBWNLDH-UHFFFAOYSA-N 3,6-dimethylcyclohexene Chemical compound CC1CCC(C)C=C1 ADPYSZNUBWNLDH-UHFFFAOYSA-N 0.000 description 2
- 101100322245 Caenorhabditis elegans des-2 gene Proteins 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- GMEABEUGZLUWGD-UHFFFAOYSA-M [Na+].N(c1ccccc1)c1ccccc1.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Na+].N(c1ccccc1)c1ccccc1.CCCCCCCCCCCCCCCCCC([O-])=O GMEABEUGZLUWGD-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- LRIUTQPZISVIHK-FNORWQNLSA-N (3e)-tetradeca-1,3-diene Chemical compound CCCCCCCCCC\C=C\C=C LRIUTQPZISVIHK-FNORWQNLSA-N 0.000 description 1
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- TXNWMICHNKMOBR-UHFFFAOYSA-N 1,2-dimethylcyclohexene Chemical compound CC1=C(C)CCCC1 TXNWMICHNKMOBR-UHFFFAOYSA-N 0.000 description 1
- NQIVPQHOBXSALG-UHFFFAOYSA-N 1-(2-methylpropyl)cyclohexene Chemical compound CC(C)CC1=CCCCC1 NQIVPQHOBXSALG-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- INNYVOGDZSDNIP-UHFFFAOYSA-N 1-butylcyclohexene Chemical compound CCCCC1=CCCCC1 INNYVOGDZSDNIP-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- QIUCYKBVFAPWRR-UHFFFAOYSA-N 1-ethenoxy-3-methylbutane Chemical compound CC(C)CCOC=C QIUCYKBVFAPWRR-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- IFVMAGPISVKRAR-UHFFFAOYSA-N 1-ethylcyclohexene Chemical compound CCC1=CCCCC1 IFVMAGPISVKRAR-UHFFFAOYSA-N 0.000 description 1
- ZYMCVIZKLGUPBG-UHFFFAOYSA-N 1-propan-2-ylcyclohexene Chemical compound CC(C)C1=CCCCC1 ZYMCVIZKLGUPBG-UHFFFAOYSA-N 0.000 description 1
- WCPWJMLXSZIWOP-UHFFFAOYSA-N 1-propylcyclohexene Chemical compound CCCC1=CCCCC1 WCPWJMLXSZIWOP-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- UZPWKTCMUADILM-UHFFFAOYSA-N 3-methylcyclohexene Chemical compound CC1CCCC=C1 UZPWKTCMUADILM-UHFFFAOYSA-N 0.000 description 1
- HDIHOAXFFROQHR-UHFFFAOYSA-N 6-aminohexylcarbamic acid Chemical compound NCCCCCCNC(O)=O HDIHOAXFFROQHR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QTHCDCUNMXEZCS-UHFFFAOYSA-N C(=C)C=1C=CC=C(CCl)C1.C(=C)OCCCl Chemical compound C(=C)C=1C=CC=C(CCl)C1.C(=C)OCCCl QTHCDCUNMXEZCS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000952234 Homo sapiens Sphingolipid delta(4)-desaturase DES1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 101000855847 Mus musculus Cytohesin-3 Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 102100037416 Sphingolipid delta(4)-desaturase DES1 Human genes 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- ANTNQGGUTAZUIC-UHFFFAOYSA-N ethenyl 2-cyanoacetate Chemical compound C=COC(=O)CC#N ANTNQGGUTAZUIC-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005179 haloacetyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- VYPDUQYOLCLEGS-UHFFFAOYSA-M sodium;2-ethylhexanoate Chemical compound [Na+].CCCCC(CC)C([O-])=O VYPDUQYOLCLEGS-UHFFFAOYSA-M 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
Definitions
- the present invention relates to an acrylic rubber composition, and more particularly to an acrylic rubber composition capable of giving vulcanization products having an improved compression set.
- Known typical vulcanizable, halogen-containing acrylic rubber systems are those based on polyamine or its carbamate.
- the resulting vulcanization products still have such disadvantages as a poor compression set and a poor resistance to heat ageing.
- it was proposed to copolymerize acrylic rubber with a cross-linking site monomer containing an active halogen such as vinyl chloroacetate, etc. JP-B-39-20515.
- Such known active halogen-containing acrylic rubber vulcanizable systems contain a vulcanizer system of fatty acid alkali metal salt/sulfur or a vulcanizer system of trithiocyanuric acid/alkyldithiocarbamic acid metal salt.
- the former vulcanizer system can give vulcanization products having good normal state physical properties and a good resistance to heat ageing, but a poor compression set.
- the latter vulcanizer system capable of giving vulcanization products having a good compression set has been practically used up to now as a leading vulcanizer system for use in the vulcanization molding of O-rings, gaskets, etc. requiring a good compression set.
- the vulcanizer system of trithiocyanuric acid/alkyldithiocarbamic acid metal salt still has the following problems, one of which is generation of unpleasant odor from alkyldithiocarbamic acid metal salt during the vulcanization. Furthermore, in the rubber molding and processing fields, a shift from the now leading press molding to the injection molding is under way to increase the productivity, but this vulcanizer system has a problem of poor injection moldability.
- an unsaturated monocarboxylic acid ester such as acrylic acid esters
- acrylic acid esters have problems not only of generation of unpleasant odor and skin irritation during the kneading or vulcanization, but also of considerably retarded vulcanization and lowered modulus or breaking strength, and derioration of mold releasability due to the retarded vulcanization.
- An object of the present invention is to provide a halogen-containing acrylic rubber composition capable of giving vulcanization products having an improved compression set without substantial deterioration of normal state physical properties, a resistance to heat ageing, etc.
- Another object of the present invention is to provide a halogen-containing acrylic rubber composition without generation of unpleasant odor or skin irritation and without lowering of mold releasability during the vulcanization or molding.
- an acrylic rubber composition which comprises a halogen-containing acrylic rubber, a vulcanizing agent and at least one unsaturated compound selected from the group consisting of (1) ⁇ -olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters.
- Halogen-containing acrylic rubber for use in the present invention includes, for example, copolymers of at least one main component selected from alkyl, acrylate, alkoxyalkyl acrylate, alkylthioalkyl acrylate, cyanoalkyl acrylate, etc.
- halogen-containing monomer selected from (1) 2-chloroethyl vinyl ether, 2-chloroethyl acrylate and vinyl benzyl chloride, (2) vinyl chloroacetate and allyl chloroacetate, (3) addition reaction products of a glycidyl compound such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.
- the copolymers can contain not more than about 30% by weight of other ordinary vinyl compounds as copolymerized therein.
- Acrylic copolymers containing lactone-modified acrylate (JP-A-63-264612) or terminal cyanolactone-modified acrylate (JP-A-1-123809), or the like, as copolymerized therein, can be also used in the present invention.
- halogen- and carboxyl-containing acrylic rubber for example, the above-mentioned halogen-containing acrylic rubber further containing about 0.1 to about 10% by weight, preferably about 1 to about 5% by weight, of an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, maleic acid, etc. or an unsaturated dicarboxylic acid monoester such as mono lower alkyl maleate, etc., as copolymerized therein, can be used in the present invention as the halogen-containing acrylic rubber.
- an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, maleic acid, etc. or an unsaturated dicarboxylic acid monoester such as mono lower alkyl maleate, etc.
- halogen-containing acrylic rubbers can be vulcanized preferably with the following vulcanizer systems:
- Aliphatic acid alkali metal salts include lithium salts, potassium salts, sodium salts, etc. of saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, aliphatic dicarboxylic acids, aromatic dicarboxy acids, etc. and more specifically include, for example, potassium stearate, sodium stearate, potassium oleate, sodium oleate, sodium 2-ethylhexanoate, sodium potassium tartrate, sodium propionate, sodium acetate, etc. Particularly preferable are sodium or potassium salts of fatty acids having 8 to 18 carbon atoms. Potassium salts generally have a tendency to accelerate the vulcanization rate.
- Vulcanizer system of trithiocyanuric acid/aliphatic acid alkali metal salt (b) Vulcanizer system of trithiocyanuric acid/aliphatic acid alkali metal salt:
- Hexamethylenediamine or its carbamate is preferably used as the diamine or its carbamate.
- vulcanizer sysrtems can be also used:
- 0.1 to about 10 parts by weight preferably about 0.2 to about 1 parts by weight or about 1 to about 5 parts by weight, depending on vulcanizer components and their combination, of one of these vulcanizer systems is used per 100 parts by weight of the halogen-containing acrylic rubber.
- the present acrylic rubber composition comprising the above-mentioned halogen-containing acrylic rubber and vulcanizing agent contains at least one unsaturated compound selected from the group consisting of the following compounds (1) to (5):
- ⁇ -olefins having at least 4 carbon atoms (1) ⁇ -olefins having at least 4 carbon atoms:
- ⁇ -olefins having at least 4 carbon atoms, usually 4 to 30 carbon atoms and preferably 6 to 20 carbon atoms, where the ⁇ -olefins are in a liquid state are used.
- ⁇ -olefins having such carbon atoms are oligomers obtainable as low-molecular weight polymers of ethylene monomer and are mixtures of oligomers having various degree of polymerization.
- ⁇ -olefins are used as such, or are used as ⁇ -olefins having a narrow distribution of carbon atoms on purification.
- ⁇ -olefins having less than 4 carbon atoms have too low a boiling point and are dissipated during the vulcanization.
- ⁇ -olefins having a longer carbon chain are in a wax state and are hard to handle.
- ⁇ -olefins contain branched olefins, internal olefins or saturated hydrocarbons, but can be used as such without any trouble.
- ⁇ -olefins About 0.1 to about 30 parts by weight of at least one of these ⁇ -olefins is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the ⁇ -olefins is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the ⁇ -olefins can be used together with various plasticizers whereby the compression set can be effectively improved.
- the use of ⁇ -olefins have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid ester and also have no mold releasability problem.
- Carboxylic acid vinyl esters for use in the present invention can be represented by the general formula RCOOCH ⁇ CH 2 , where R is an alkyl group having 1 to 20 carbon atoms, preferably 3 to 13 carbon atoms or an aryl group, and the alkyl group or aryl group may take a substituent group such as cyano group, alkoxy group, etc.
- Such carboxylic acid vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyanoacetate, vinyl benzoate, etc.
- carboxylic acid vinyl esters About 0.1 to about 30 parts by weight of at least one of these carboxylic acid vinyl esters is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the carboxylic acid vinyl esters is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the carboxylic acid vinyl esters can be used together with various plasticizers, whereby the compression set can be effectively improved.
- the use of carboxylic acid vinyl esters have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid ester and also have no mold releasability problem.
- Alkyl vinyl ethers for use in the present invention are those represented by the general formula ROCH ⁇ CH 2 where R is an alkyl group having 3 to 18 carbon atoms, preferably 5 to 18 carbon atoms.
- R is an alkyl group having 3 to 18 carbon atoms, preferably 5 to 18 carbon atoms.
- Alkyl vinyl ethers having an alkyl group having less than 3 carbon atoms have too low a boiling point and are dissipated during the vulcanization. That is, the effect is reduced by half.
- the alkyl group may further have such a substituent as alkoxy group, etc.
- the alkyl vinyl ether for use in the present invention includes, for example, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-amyl vinyl ether, isoamyl vinyl ether, 2-ethylhexyl vinyl ether, n-octadecyl vinyl ether, etc.
- alkyl vinyl ethers About 0.1 to about 30 parts by weight of at least one of these alkyl vinyl ethers is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the alkyl vinyl ethers is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the alkyl vinyl ethers can be used together with various plasticizers, whereby the compression set can be effectively improved.
- the use of alkyl vinyl ethers have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid esters and also have no mold releasability problem.
- Lower alkyl cyclohexenes for use in the present invention are cyclohexenes, at least one of whose hydrogen atoms at the 3-, 4-, 5- or 6- positions excluding the unsaturated bond is replaced with a lower alkyl group.
- the lower alkyl group may further have a lower alkoxy group, etc. as substituents, that is, it may be a lower alkoxy-lower alkyl group, etc.
- the lower alkyl cyclohexenes include, for example, methylcyclohexene, dimethylcyclohexene, ethylcyclohexene, n-propylcyclohexene, isopropylcyclohexene, n-butylcyclohexene, isobutylcyclohexene, t-buty lcyclohexene, etc.
- Position of substitution for the lower alkyl group can be any one of 3- to 6-positions.
- Cyclohexenecarboxylic acid caprolactone esters for use in the present invention include cyclohexenes having a caprolactone ester group represented by the following general formula at the 3-position:
- R is an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an alkoxyalkyl group or a cyclohexenyl group and n is an integer of 1 to 5.
- halogen-containing acrylic rubber About 0.1 to about 30 parts by weight of at least one of these lower alkylcyclohexenes or cyclohexenecarboxylic acid caprolactone esters is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the lower alkylcyclohexenes or cyclohexenecarboxylic acid caprolactone esters is used per 100 parts by weight of the halogen-containing acrylic rubber.
- Unsaturated dicarboxylic acid diesters for use in the present invention are diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc., with two alkyl groups or two alkenyl groups, each having 1 to 10 carbon atoms, that is, such as dialkyls or dialkenyls as dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, diisobutyl, di-t-butyl, di-2-ethylhexyl, dioctyl, diallyl, etc.
- the diesters usually have the same ester groups, but can have mutually different ester groups.
- the alkyl groups may be alkoxy-substituted alkyl groups, such as methoxymethyl group, ethoxymethyl group, methoxyethyl group and ethoxyethyl group.
- 0.1 to about 30 parts by weight of at least one of these unsaturated dicarboxylic acid diesters is used per 100 parts by weight of halogen-containing acrylic rubber.
- about 1 to about 3 parts by weight of the unsaturated dicarboxylic acid diesters is used per 100 parts by weight of the halogen-containing acrylic rubber.
- even about 10 to about 30 parts by weight of the unsaturated dicarboxylic acid diesters can be used together with various plasticizers, whereby the compression set can be effectively improved.
- Unsaturated dicarboxylic acid diesters have higher molecular weights and boiling points than those of acrylic acid esters and thus have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid esters and also have no mold releasability problem.
- the halogen-containing acrylic rubber composition comprising the above-mentioned essential components can further contain other necessary additives such as a filler, a reinforcing agent, a vulcanization acid, a lubricant, etc. when desired.
- the composition can contain carbon black for the O-ring and packing purposes, and can contain diatomaceous earth, white carbon, etc. for the oil seal purpose.
- the present composition can be prepared in a closed type kneader such as a kneader and a Bumbury mixer or in an open-type kneader such as an open roll, and its vulcanization can be carried out usually by press vulcanization or injection molding vulcanization at a temperature of about 150 to about 250° C. for about 1 to about 30 minutes, and if required, secondary vulcanization can be carried out by oven vulcanization or steam vulcanization at a temperature of about 150 to about 200° C. for about 1 to about 22 hours.
- Compression set of vulcanization products can be improved without any substantial deterioration of normal state physical properties or resistance to heat ageing by adding at least one unsaturated compound selected from the group consisting of (1) ⁇ -olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters to a composition comprising a halogen-containing acrylic rubber and a vulcanizing agent.
- unsaturated compound selected from the group consisting of (1) ⁇ -olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters to a composition comprising
- Acrylic rubber compositions were prepared from polymers A to D having monomer compositions (% by weight) given in the following Table 1, according to formulations (parts by weight) given in the following Table 2 by kneading in an 8-inch open roll.
- compositions were subjected to measurement of Mooney viscosity and scorch time according to JIS K-6300. Furthermore, the compositions were subjected to press vulcanization at 180° C. for 8 minutes and then to oven vulcanization at 175° C. for 4 hours, and the resulting vulcanization products were subjected to determination of normal state physical properties, resistance to heat ageing and compression set according to JIS K-6301. Test conditions for the resistance to heat ageing were 175° C. for 70 hours and those for the compression set were 150° C., for 70 hours. Results of determination are shown in the following Table 3.
- Acrylic rubber compositions were prepared from polymers E given in the foregoing Table 1, according to formulations given in the following Table 4 by kneading in an 8-inch open roll.
- Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the same amount of vinyl acetate was used in place of hexene, by kneading in an 8-inch open roll. Properties of unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 6.
- Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of vinyl laurate, the hexene with the same amount of vinyl acetate and the ⁇ -olefin with the same amount of vinyl pivalate, by kneading in an 8-inch open roll.
- Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 7.
- Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the hexene was replaced with the same amount of n-amyl vinyl ether, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 8.
- Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of n-octadecyl vinyl ether, the hexene with the same amount of n-amyl vinyl ether and the ⁇ -olefin with the same amount of n-isoamyl vinyl ether, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 9.
- Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Examples 1 to 6, except that the hexene was replaced with the same amount of 3,6-dimethylcyclohexene, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 10.
- Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of 3-methylcyclohexene, the hexene with the same amount of 3,6-dimethylcyclohexene and the ⁇ -olefin with the same amount of caprolactone-modified cyclohexene (CLM3, trademark of a product made by Daicel Kagaku K. K., Japan), by kneading in an 8-inch open roll.
- Properties of the thus prepared compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 11.
- Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the hexene was replaced with the same amount of dibutyl fumarate (DEs-2, trademark of a product made by Kurogane Kasei K. K., Japan), by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table
- Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of dibutyl maleate (DEs-1, trademark of a product made by Kurogane Kasei K. K., Japan), the hexene with the same amount of dibutyl fumarate (DEs-2) and the ⁇ -olefin with the same amount of dibutyl itaconate (DEs-3, trademark of a product made by Kurogane Kasei K. K., Japan), by kneading in an 8-inch open roll.
- Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 13.
- Acrylic rubber compositions were prepared from the polymer C or D, according to the following formulations given in the following Table 14 by kneading in an 8-inch open roll.
- Acrylic rubber compositions were prepared from the polymer E, according to formulations given in the following Table 16 by kneading in an 8-inch open roll.
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Abstract
An acrylic rubber composition comprising a halogen-containing acrylic rubber, a vulcanizing agent and at least one unsaturated compound selected from the group consisting of (1) α-olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters can give vulcanization products having an improved compression set without any substantial deterioration of normal state physical properties and resistance to heat ageing of the vulcanization products, where the unsaturated compound gives off no unpleaseant odor without any skin irritation when vulcanized and without lowering the mold releasability.
Description
1. Field of the Invention
The present invention relates to an acrylic rubber composition, and more particularly to an acrylic rubber composition capable of giving vulcanization products having an improved compression set.
2. Related Prior Art
Known typical vulcanizable, halogen-containing acrylic rubber systems are those based on polyamine or its carbamate. The resulting vulcanization products still have such disadvantages as a poor compression set and a poor resistance to heat ageing. To improve these disadvantages, it was proposed to copolymerize acrylic rubber with a cross-linking site monomer containing an active halogen such as vinyl chloroacetate, etc. (JP-B-39-20515).
Such known active halogen-containing acrylic rubber vulcanizable systems contain a vulcanizer system of fatty acid alkali metal salt/sulfur or a vulcanizer system of trithiocyanuric acid/alkyldithiocarbamic acid metal salt. The former vulcanizer system can give vulcanization products having good normal state physical properties and a good resistance to heat ageing, but a poor compression set. Thus, the latter vulcanizer system capable of giving vulcanization products having a good compression set has been practically used up to now as a leading vulcanizer system for use in the vulcanization molding of O-rings, gaskets, etc. requiring a good compression set.
However, the vulcanizer system of trithiocyanuric acid/alkyldithiocarbamic acid metal salt still has the following problems, one of which is generation of unpleasant odor from alkyldithiocarbamic acid metal salt during the vulcanization. Furthermore, in the rubber molding and processing fields, a shift from the now leading press molding to the injection molding is under way to increase the productivity, but this vulcanizer system has a problem of poor injection moldability.
To improve the poor compression set of the vulcanizer system of fatty acid alkali metal salt/sulfur capable of giving vulcanization products having good normal state physical properties, a good resistance to heat ageing and having a good injection moldability without generation of unpleasant odor, on the other hand, it was proposed to incorporate an N-substituted bismaleimide into the vulcanizer system (JP-B-48-24019). The proposed vulcanizer system has an improved compression set indeed, but has too high a vulcanization rate and a cross-linking density, resulting in deterioration of breaking strength, (stress strength at break) breaking elongation, (elongation at break) etc.
It was also proposed to add an unsaturated monocarboxylic acid ester such as acrylic acid esters to the vulcanizer system of fatty acid alkali metal salt/sulfur (JP-A-3-31351). However, the acrylic acid esters have problems not only of generation of unpleasant odor and skin irritation during the kneading or vulcanization, but also of considerably retarded vulcanization and lowered modulus or breaking strength, and derioration of mold releasability due to the retarded vulcanization.
Furthermore, it was proposed to add a thioether compound to the vulcanizer system (JP-A-4-142356). Generally, the resistance to heat ageing of acrylic rubber is connected to a brittling tendency and only available effective antioxidants for relieving the brittling tendency are specific amine-based antioxidants. Thus, even use of a thioether compound in place of the amine-based antioxidant inevitably gives vulcanization products having a poor resistance to heat ageing.
An object of the present invention is to provide a halogen-containing acrylic rubber composition capable of giving vulcanization products having an improved compression set without substantial deterioration of normal state physical properties, a resistance to heat ageing, etc.
Another object of the present invention is to provide a halogen-containing acrylic rubber composition without generation of unpleasant odor or skin irritation and without lowering of mold releasability during the vulcanization or molding.
According to the present invention, there is provided an acrylic rubber composition which comprises a halogen-containing acrylic rubber, a vulcanizing agent and at least one unsaturated compound selected from the group consisting of (1) α-olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters.
Halogen-containing acrylic rubber for use in the present invention includes, for example, copolymers of at least one main component selected from alkyl, acrylate, alkoxyalkyl acrylate, alkylthioalkyl acrylate, cyanoalkyl acrylate, etc. in an amount of about 60 to about 99.8% by weight on the basis of total copolymer, copolymerized with about 0.1 to about 10% by weight, preferably about 1 to about 5% by weight, of at least one cross-linking site, halogen-containing monomer selected from (1) 2-chloroethyl vinyl ether, 2-chloroethyl acrylate and vinyl benzyl chloride, (2) vinyl chloroacetate and allyl chloroacetate, (3) addition reaction products of a glycidyl compound such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. with monochloroacetic acid and (4) alkenyl esters of α- or β-halogen-substituted aliphatic monocarboxylic acids; haloalkyl esters, haloalkyl alkenyl esters, haloalkyl alkenyl ketones and haloacetoxyalkyl esters of (meth)acrylic acid; and haloacetyl-containing unsaturated compounds. The copolymers can contain not more than about 30% by weight of other ordinary vinyl compounds as copolymerized therein. Acrylic copolymers containing lactone-modified acrylate (JP-A-63-264612) or terminal cyanolactone-modified acrylate (JP-A-1-123809), or the like, as copolymerized therein, can be also used in the present invention.
Furthermore, halogen- and carboxyl-containing acrylic rubber, for example, the above-mentioned halogen-containing acrylic rubber further containing about 0.1 to about 10% by weight, preferably about 1 to about 5% by weight, of an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, maleic acid, etc. or an unsaturated dicarboxylic acid monoester such as mono lower alkyl maleate, etc., as copolymerized therein, can be used in the present invention as the halogen-containing acrylic rubber.
These halogen-containing acrylic rubbers can be vulcanized preferably with the following vulcanizer systems:
(a) Vulcanizer system of aliphatic acid alkali metal salt/sulfur:
Aliphatic acid alkali metal salts include lithium salts, potassium salts, sodium salts, etc. of saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, aliphatic dicarboxylic acids, aromatic dicarboxy acids, etc. and more specifically include, for example, potassium stearate, sodium stearate, potassium oleate, sodium oleate, sodium 2-ethylhexanoate, sodium potassium tartrate, sodium propionate, sodium acetate, etc. Particularly preferable are sodium or potassium salts of fatty acids having 8 to 18 carbon atoms. Potassium salts generally have a tendency to accelerate the vulcanization rate.
(b) Vulcanizer system of trithiocyanuric acid/aliphatic acid alkali metal salt:
The same aliphatic acid alkali metal salts as mentioned in the above item (a) can be used in this vulcanizer system.
(c) Vulcanizer system of diamine or its carbamate/dibasic lead phosphite:
Hexamethylenediamine or its carbamate is preferably used as the diamine or its carbamate.
Besides, the following vulcanizer sysrtems can be also used:
(d) Vulcanizer system of trithiocyanuric acid/dicyandiamide/dibasic lead phosphite
(e) Vulcanizer system of trithiocyanuric acid/dicyandiamide/metal oxide
(f) Vulcanizer system of trithiocyanuric acid/dicyandiamide/aluminum-containing compound
(g) Vulcanizer system of trithiocyanuric acid/dicyandiamide/aliphatic acid alkaline earth metal salt or zinc salt
(h) Vulcanizer system of trithiocyanuric acid/metal dithiocarbamate/thiuram sulfide
(i) Vulcanizer system of trithiocyanuric acid/metal dithiocarbamate/quaternary ammonium or phosphonium salt
(j) Vulcanizer system of trithiocyanuric acid/trimethyl-thiourea/metal oxide
(k) Vulcanizer system of trithiocyanuric acid/aliphatic acid alkaline earth metal salt or zinc salt
Usually about 0.1 to about 10 parts by weight, preferably about 0.2 to about 1 parts by weight or about 1 to about 5 parts by weight, depending on vulcanizer components and their combination, of one of these vulcanizer systems is used per 100 parts by weight of the halogen-containing acrylic rubber.
The present acrylic rubber composition comprising the above-mentioned halogen-containing acrylic rubber and vulcanizing agent contains at least one unsaturated compound selected from the group consisting of the following compounds (1) to (5):
(1) α-olefins having at least 4 carbon atoms:
α-olefins having at least 4 carbon atoms, usually 4 to 30 carbon atoms and preferably 6 to 20 carbon atoms, where the α-olefins are in a liquid state, are used. Generally, α-olefins having such carbon atoms are oligomers obtainable as low-molecular weight polymers of ethylene monomer and are mixtures of oligomers having various degree of polymerization. In the present invention, α-olefins are used as such, or are used as α-olefins having a narrow distribution of carbon atoms on purification. α-olefins having less than 4 carbon atoms have too low a boiling point and are dissipated during the vulcanization. That is, the effect is reduced by half. On the other hand, α-olefins having a longer carbon chain are in a wax state and are hard to handle. Sometimes, α-olefins contain branched olefins, internal olefins or saturated hydrocarbons, but can be used as such without any trouble.
About 0.1 to about 30 parts by weight of at least one of these α-olefins is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the α-olefins is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the α-olefins can be used together with various plasticizers whereby the compression set can be effectively improved. The use of α-olefins have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid ester and also have no mold releasability problem.
(2) Carboxylic acid vinyl esters:
Carboxylic acid vinyl esters for use in the present invention can be represented by the general formula RCOOCH═CH2, where R is an alkyl group having 1 to 20 carbon atoms, preferably 3 to 13 carbon atoms or an aryl group, and the alkyl group or aryl group may take a substituent group such as cyano group, alkoxy group, etc. Such carboxylic acid vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyanoacetate, vinyl benzoate, etc.
About 0.1 to about 30 parts by weight of at least one of these carboxylic acid vinyl esters is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the carboxylic acid vinyl esters is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the carboxylic acid vinyl esters can be used together with various plasticizers, whereby the compression set can be effectively improved. The use of carboxylic acid vinyl esters have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid ester and also have no mold releasability problem.
(3) Alkyl vinyl ethers:
Alkyl vinyl ethers for use in the present invention are those represented by the general formula ROCH═CH2 where R is an alkyl group having 3 to 18 carbon atoms, preferably 5 to 18 carbon atoms. Alkyl vinyl ethers having an alkyl group having less than 3 carbon atoms have too low a boiling point and are dissipated during the vulcanization. That is, the effect is reduced by half. The alkyl group may further have such a substituent as alkoxy group, etc. The alkyl vinyl ether for use in the present invention includes, for example, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-amyl vinyl ether, isoamyl vinyl ether, 2-ethylhexyl vinyl ether, n-octadecyl vinyl ether, etc.
About 0.1 to about 30 parts by weight of at least one of these alkyl vinyl ethers is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the alkyl vinyl ethers is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the alkyl vinyl ethers can be used together with various plasticizers, whereby the compression set can be effectively improved. The use of alkyl vinyl ethers have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid esters and also have no mold releasability problem.
(4) Lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters:
Lower alkyl cyclohexenes for use in the present invention are cyclohexenes, at least one of whose hydrogen atoms at the 3-, 4-, 5- or 6- positions excluding the unsaturated bond is replaced with a lower alkyl group. The lower alkyl group may further have a lower alkoxy group, etc. as substituents, that is, it may be a lower alkoxy-lower alkyl group, etc. The lower alkyl cyclohexenes include, for example, methylcyclohexene, dimethylcyclohexene, ethylcyclohexene, n-propylcyclohexene, isopropylcyclohexene, n-butylcyclohexene, isobutylcyclohexene, t-buty lcyclohexene, etc. Position of substitution for the lower alkyl group can be any one of 3- to 6-positions. Cyclohexenecarboxylic acid caprolactone esters for use in the present invention include cyclohexenes having a caprolactone ester group represented by the following general formula at the 3-position:
--COO (CH2 )5 COO!nCH2 R
where R is an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an alkoxyalkyl group or a cyclohexenyl group and n is an integer of 1 to 5.
About 0.1 to about 30 parts by weight of at least one of these lower alkylcyclohexenes or cyclohexenecarboxylic acid caprolactone esters is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the lower alkylcyclohexenes or cyclohexenecarboxylic acid caprolactone esters is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters can be used together with various plasticizers, whereby the compression set can be effectively improved. The use of lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid esters and also have no mold releasability problem.
(5) Unsaturated dicarboxylic acid diesters:
Unsaturated dicarboxylic acid diesters for use in the present invention are diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc., with two alkyl groups or two alkenyl groups, each having 1 to 10 carbon atoms, that is, such as dialkyls or dialkenyls as dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, diisobutyl, di-t-butyl, di-2-ethylhexyl, dioctyl, diallyl, etc. The diesters usually have the same ester groups, but can have mutually different ester groups. The alkyl groups may be alkoxy-substituted alkyl groups, such as methoxymethyl group, ethoxymethyl group, methoxyethyl group and ethoxyethyl group.
About 0.1 to about 30 parts by weight of at least one of these unsaturated dicarboxylic acid diesters is used per 100 parts by weight of halogen-containing acrylic rubber. In case of application to vulcanization products requiring a low compression set such as O-rings, gaskets, etc., about 1 to about 3 parts by weight of the unsaturated dicarboxylic acid diesters is used per 100 parts by weight of the halogen-containing acrylic rubber. In case of application to hose materials, etc., even about 10 to about 30 parts by weight of the unsaturated dicarboxylic acid diesters can be used together with various plasticizers, whereby the compression set can be effectively improved. Unsaturated dicarboxylic acid diesters have higher molecular weights and boiling points than those of acrylic acid esters and thus have no such problems of unpleasant odor or skin irritation during the vulcanization as encountered in the case of acrylic acid esters and also have no mold releasability problem.
The halogen-containing acrylic rubber composition comprising the above-mentioned essential components can further contain other necessary additives such as a filler, a reinforcing agent, a vulcanization acid, a lubricant, etc. when desired. For example, in case of application to vulcanization-molding materials for various sealing materials, the composition can contain carbon black for the O-ring and packing purposes, and can contain diatomaceous earth, white carbon, etc. for the oil seal purpose.
The present composition can be prepared in a closed type kneader such as a kneader and a Bumbury mixer or in an open-type kneader such as an open roll, and its vulcanization can be carried out usually by press vulcanization or injection molding vulcanization at a temperature of about 150 to about 250° C. for about 1 to about 30 minutes, and if required, secondary vulcanization can be carried out by oven vulcanization or steam vulcanization at a temperature of about 150 to about 200° C. for about 1 to about 22 hours.
Compression set of vulcanization products can be improved without any substantial deterioration of normal state physical properties or resistance to heat ageing by adding at least one unsaturated compound selected from the group consisting of (1) α-olefins having at least 4 carbon atoms, (2) carboxylic acid vinyl esters, (3) alkyl vinyl ethers, (4) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (5) unsaturated dicarboxylic acid diesters to a composition comprising a halogen-containing acrylic rubber and a vulcanizing agent. These specific unsaturated cmpounds, as added, give off no unpleasant odor without any skin during the vulcanization and without lowering the mold releasability.
The present invention will be described in detail below, referring to Examples.
Acrylic rubber compositions were prepared from polymers A to D having monomer compositions (% by weight) given in the following Table 1, according to formulations (parts by weight) given in the following Table 2 by kneading in an 8-inch open roll.
TABLE 1
______________________________________
Comonomer\Polymer
A B C D E
______________________________________
Ethyl acrylate 98 48 95 48
Butyl acrylate 25 25 50
2-methoxyethyl acrylate 25 25 48
Vinyl chloroacetate
2 2 2
2-chloroethyl vinyl ether 5
Chloromethylstyrene 2
______________________________________
TABLE 2
______________________________________
Ex. 1
Ex. 2 Ex. 3 Ex. 4
Ex. 5
Ex. 6
______________________________________
Polymer A 100
Polymer B 100 100
Polymer C 100 100
Polymer D 100
HAF carbon black (N330)
50 60 50 50 60
FEF carbon black (N550) 65
Stearic acid 1 1 1 1 1 1
4,4'-(α,α-dimethylbenzyl)-
2 2 2 2 2 2
diphenylamine*.sup.1
Plasticizer 10
(Fatty acid metal salt)*.sup.2
Sodium stearate
2.5 3 2.5 3 3
Potassium stearate
0.25 0.25 0.5
Sulfur 0.3 0.3 0.3
Tricyanuric acid 0.6 0.6
Dibasic lead phosphite 3
Hexamethylenediamine 0.75
carbamate*.sup.3
Hexene*.sup.4 2 2 2 2 2 2
______________________________________
Remarks
*.sup.1 Nocrack CD, trademark of an antioxidant made by OuchiShinko Kagak
K. K., Japan
*.sup.2 TE80, trademark of a plasticizer made by Technical Processing
Company
*.sup.3 Cheminox AC6, trademark of a vulcanizer made by Nippon Mektron K.
K., Japan
*.sup.4 Dialene 6, trademark of hexene (C.sub.6 : more than 99%), made by
Mitsubishi Kagaku K. K., Japan
The thus obtained compositions were subjected to measurement of Mooney viscosity and scorch time according to JIS K-6300. Furthermore, the compositions were subjected to press vulcanization at 180° C. for 8 minutes and then to oven vulcanization at 175° C. for 4 hours, and the resulting vulcanization products were subjected to determination of normal state physical properties, resistance to heat ageing and compression set according to JIS K-6301. Test conditions for the resistance to heat ageing were 175° C. for 70 hours and those for the compression set were 150° C., for 70 hours. Results of determination are shown in the following Table 3.
TABLE 3
______________________________________
Ex. 1
Ex. 2 Ex. 3 Ex. 4
Ex. 5
Ex. 6
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
56 54 37 52 44 45
Scorch time (min.)
19.9 10.8 8.9 25.0 17.3 12.4
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
72 69 58 72 70 70
100% Modulus (kg/cm.sup.2)
49 52 37 47 41 48
Breaking strength (kg/cm.sup.2)
160 148 110 130 154 150
Breaking elongation (%)
320 270 280 240 330 260
Resistance to heat ageing
Hardness change (%)
+9 +9 +5 +10 +6 +6
Modulus change (%)
-11 +8 -6 +15 +14 +13
Breaking strength change (%)
-11 -5 -6 -6 0 -2
Breaking elongation change
-6 +1 -8 -5 -8 -8
(%)
Compression set (%)
22 21 32 32 20 21
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from polymers E given in the foregoing Table 1, according to formulations given in the following Table 4 by kneading in an 8-inch open roll.
TABLE 4
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
7 8 9 10 11 12
______________________________________
Polymer E 100 100 100 100 100 100
HAF carbon black (N330)
60 60 60 60 60
FEF carbon black (N550) 60
Stearic acid 1 1 1 1 1 1
4,4'-(α,α-dimethylbenzyl)-
2 2 2 2 2 2
diphenylamine
Sodium stearate
3 3 3 3 3 3
Potassium stearate
0.25 0.25 0.25 0.25 0.25 0.25
Sulfur 0.3 0.3 0.3 0.3 0.3 0.3
Octadecene*.sup.5
2
Hexene 2 0.5 5 2
α-Olefin*.sup.6 2
______________________________________
Remarks
*.sup.5 Dialene 18 (C.sub.18 : more than 97%), trademark of a product mad
by Mitsubishi Kagaku K. K., Japan
*.sup.4 Dialene 30 (C.sub.30 : more than 95%), trademark of a product mad
by Mitsubishi Kagaku K. K., Japan
Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 5.
TABLE 5
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
7 8 9 10 11 12
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
51 49 48 53 40 46
Scorch time (min.)
20.0 18.9 19.9 18.8 19.7 20.0
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
67 62 66 68 66 63
100% Modulus (kg/cm.sup.2)
60 55 61 68 52 63
Breaking strength (kg/cm.sup.2)
144 144 144 145 145 129
Breaking elongation (%)
220 220 210 190 240 180
Resistance to heat ageing
Hardness change (%)
+10 +15 +12 +10 +12 +7
Modulus change (%)
+1 +2 +7 -12 +8 -10
Breaking strength change
-7 -9 -5 -5 -7 -8
(%)
Breaking elongation change
-5 -5 0 +11 -12 +6
(%)
Compression set (%)
19 20 20 24 21 16
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the same amount of vinyl acetate was used in place of hexene, by kneading in an 8-inch open roll. Properties of unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 6.
TABLE 6
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
13 14 15 16 17 18
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
54 57 38 52 43 44
Scorch time (min.)
19.0 10.4 8.9 23.4 17.2 12.3
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
70 71 56 72 71 70
100% Modulus (kg/cm.sup.2)
48 53 38 44 41 50
Breaking strength (kg/cm.sup.2)
159 148 111 129 152 153
Breaking elongation (%)
320 280 270 240 330 270
Resistance to heat ageing
Hardness change (%)
+9 +9 +5 +7 +5 +6
Modulus change (%)
-12 +2 -12 +8 +8 +7
Breaking strength change (%)
-10 -6 -6 -5 -4 +1
Breaking elongation change
-5 +3 -8 -5 -7 -8
(%)
Compression set (%)
24 25 34 36 25 22
<Other influences of
unsaturated compounds>
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of vinyl laurate, the hexene with the same amount of vinyl acetate and the α-olefin with the same amount of vinyl pivalate, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 7.
TABLE 7
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
19 20 21 22 23 24
______________________________________
<Properties of unvulcanized
composition>
Mooney viscosity (ML.sub.1+4, M)
50 50 49 54 42 45
Scorch time (min.)
20.3 19.2 18.9 19.4 20.8 19.4
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
67 64 66 68 65 65
100% Modulus (kg/cm.sup.2)
57 56 62 66 52 61
Breaking strength (kg/cm.sup.2)
144 143 144 147 145 130
Breaking elongation (%)
220 220 210 170 230 180
Resistance to heat ageing
Hardness change (%)
+7 +13 +10 +8 +10 +5
Modulus change (%)
-4 -4 +3 -16 +4 -16
Breaking strength change (%)
-7 -8 -6 -3 -7 -8
Breaking elongation change
-2 -4 -1 +12 -10 +8
(%)
Compression set (%)
22 22 23 26 23 21
<Other influences of
unsaturated compounds>
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the hexene was replaced with the same amount of n-amyl vinyl ether, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 8.
TABLE 8
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
25 26 27 28 29 30
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
55 56 36 51 44 45
Scorch time (min.)
18.7 10.3 9.0 23.0 16.0 13.2
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
71 70 57 73 71 70
100% Modulus (kg/cm.sup.2)
48 52 36 45 42 49
Breaking strength (kg/cm.sup.2)
160 148 109 129 153 152
Breaking elongation (%)
330 280 270 250 320 270
Resistance to heat ageing
Hardness change (%)
+8 +9 +4 +7 +5 +4
Modulus change (%)
-13 +2 -12 +9 +8 +7
Breaking strength change (%)
-10 -6 -6 -6 -4 +1
Breaking elongation change
-5 +3 -9 -5 -7 -8
(%)
Compression set (%)
24 24 35 35 24 23
<Other influences of
unsaturated compounds>
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of n-octadecyl vinyl ether, the hexene with the same amount of n-amyl vinyl ether and the α-olefin with the same amount of n-isoamyl vinyl ether, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 9.
TABLE 9
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
31 32 33 34 35 36
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
51 49 49 53 41 47
Scorch time (min.)
19.9 19.0 18.9 18.1 19.7 20.4
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
68 63 66 67 65 64
100% Modulus (kg/cm.sup.2)
58 56 61 67 53 62
Breaking strength (kg/cm.sup.2)
143 143 145 147 145 132
Breaking elongation (%)
230 220 210 190 230 170
Resistance to heat ageing
Hardness change (%)
+8 +13 +10 +8 +11 +6
Modulus change (%)
-5 -4 +3 -16 +3 -16
Breaking strength change (%)
-7 -8 -5 -4 -7 -7
Breaking elongation change
-2 -5 0 +11 -10 +8
(%)
Compression set (%)
22 23 22 27 24 20
<Other influences of
unsaturated compounds>
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Examples 1 to 6, except that the hexene was replaced with the same amount of 3,6-dimethylcyclohexene, by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 10.
TABLE 10
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
37 38 39 40 41 42
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
57 56 40 53 46 46
Scorch time (min.)
19.9 9.8 8.7 23.7 18.2 12.2
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
72 70 60 71 70 72
100% Modulus (kg/cm.sup.2)
51 53 39 48 42 50
Breaking strength (kg/cm.sup.2)
161 146 108 132 153 150
Breaking elongation (%)
330 270 290 230 330 250
Resistance to heat ageing
Hardness change (%)
+9 +10 +5 +9 +6 +7
Modulus change (%)
-10 +8 -6 +15 +13 +14
Breaking strength change (%)
-11 -5 -4 -4 0 -3
Breaking elongation change
-6 +1 -8 -4 -9 -8
(%)
Compression set (%)
28 28 36 37 36 27
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of 3-methylcyclohexene, the hexene with the same amount of 3,6-dimethylcyclohexene and the α-olefin with the same amount of caprolactone-modified cyclohexene (CLM3, trademark of a product made by Daicel Kagaku K. K., Japan), by kneading in an 8-inch open roll. Properties of the thus prepared compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 11.
TABLE 11
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
43 44 45 46 47 48
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
52 50 50 55 43 48
Scorch time (min.)
21.3 18.3 19.8 19.4 20.0 19.9
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
68 63 66 69 68 63
100% Modulus (kg/cm.sup.2)
62 55 61 68 53 63
Breaking strength (kg/cm.sup.2)
145 144 144 146 145 129
Breaking elongation (%)
220 210 210 190 230 180
Resistance to heat ageing
Hardness change (%)
+9 +14 +12 +10 +11 +7
Modulus change (%)
+2 +3 +5 -12 +9 -11
Breaking strength change (%)
-8 -9 -4 -6 -7 -9
Breaking elongation change
-4 -3 +1 +12 -11 +6
(%)
Compression set (%)
25 26 26 29 27 20
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
Skin irritation
none none none none none none
Deterioration of mold
none none none none none none
releasability
______________________________________
Acrylic rubber compositions were prepared from the same polymers A to D according to the same formulations as in Example 1 to 6, except that the hexene was replaced with the same amount of dibutyl fumarate (DEs-2, trademark of a product made by Kurogane Kasei K. K., Japan), by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table
TABLE 12
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
49 50 51 52 53 54
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
51 48 32 45 38 40
Scorch time (min.)
19.9 11.2 9.4 24.1 17.8 12.2
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
68 66 53 68 65 66
100% Modulus (kg/cm.sup.2)
45 57 39 44 47 44
Breaking strength (kg/cm.sup.2)
158 148 109 132 152 150
Breaking elongation (%)
340 280 300 250 330 270
Resistance to heat ageing
Hardness change (%)
+11 +12 +8 +13 +8 +9
Modulus change (%)
0 +16 +4 +21 +22 +21
Breaking strength change (%)
-20 -15 -16 -17 -8 -12
Breaking elongation change
-9 -2 -11 -9 -10 -12
(%)
Compression set (%)
22 22 33 32 21 22
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
______________________________________
Acrylic rubber compositions were prepared from the same polymer E according to the same formulations as in Examples 7 to 12, except that the octadecene was replaced with the same amount of dibutyl maleate (DEs-1, trademark of a product made by Kurogane Kasei K. K., Japan), the hexene with the same amount of dibutyl fumarate (DEs-2) and the α-olefin with the same amount of dibutyl itaconate (DEs-3, trademark of a product made by Kurogane Kasei K. K., Japan), by kneading in an 8-inch open roll. Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are shown in the following Table 13.
TABLE 13
______________________________________
Ex. Ex. Ex. Ex. Ex. Ex.
55 56 57 58 59 60
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
45 44 46 48 35 40
Scorch time (min.)
19.5 19.9 20.1 18.3 20.3 19.9
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
63 62 62 64 62 58
100% Modulus (kg/cm.sup.2)
55 56 54 63 48 58
Breaking strength (kg/cm.sup.2)
144 145 144 144 145 130
Breaking elongation (%)
240 240 250 220 250 210
Resistance to heat ageing
Hardness change (%)
+13 +13 +12 +13 +15 +10
Modulus change (%)
+10 +9 +10 -4 +16 -2
Breaking strength change (%)
-13 -12 -13 -14 -16 -16
Breaking elongation change
-8 -5 -6 +7 -14 +1
(%)
Compression set (%)
20 20 21 24 20 16
<Other influences of
unsaturated compounds>
Unpleasant odor
none none none none none none
______________________________________
Acrylic rubber compositions were prepared from the polymer C or D, according to the following formulations given in the following Table 14 by kneading in an 8-inch open roll.
TABLE 14
______________________________________
Comp. Ex. 1
Comp. Ex. 2
Comp. Ex. 3
______________________________________
Polymer C 100 100
Polymer D 100
HAF carbon black (N330)
56 50 60
Stearic acid 1 1 1
4,4'-(α,α-dimethylbenzyl)-
2 2 2
diphenylamine
Sodium stearate 3 3
Trithiocyanuric acid 0.6 0.6
Dibasic lead phosphite
3
Hexamethylenediamine
0.75
carbamate*.sup.3
______________________________________
Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 15.
TABLE 15
______________________________________
Comp. Comp. Comp.
Ex. 1 Ex. 2 Ex. 3
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
57 49 49
Scorch time (min.)
23.0 16.0 11.9
<Vulcanization product
properties>
Normal state physical properties
Hardness (JIS-A, pts)
75 70 69
100% Modulus (kg/cm.sup.2)
52 46 52
Breaking strength (kg/cm.sup.2)
125 155 150
Breaking elongation (%)
220 310 250
Resistance to heat ageing
Hardness change (%)
+7 +3 +7
Breaking strength change (%)
-4 -2 -2
Breaking elongation change (%)
+1 -4 -6
Compression set (%)
40 28 25
______________________________________
Acrylic rubber compositions were prepared from the polymer E, according to formulations given in the following Table 16 by kneading in an 8-inch open roll.
TABLE 16
______________________________________
Comparative Examples
4 5 6 7 8 9
______________________________________
Polymer E 100 100 100 100 100 100
HAF carbon black (N330)
60 60 60 60 60
FEF carbon black (N550) 65
Stearic acid 1 1 1 1 1 1
4,4'-(α,α-dimethylbenzyl)-
2 2 2 2 2 2
diphenylamine
Plasticizer 10
(fatty acid metal salt)
Sodium stearate
3 3 3 3 2.5
Potassium stearate
0.25 0.25 0.25 0.25 0.5
Sulfur 0.3 0.3 0.3 0.3 0.3
Trithiocyanuric acid 0.5
Zinc di-n-butylthio- 1.5
carbamate*.sup.7
Dodecyl acrylate 2
Tetradecadiene 2
Dodecane 2
______________________________________
Remarks
*.sup.7 Knoccelar BZ trademark of a vulcanization accelerator made by
OuchiShinko Kagaku Kogyo K. K., Japan
Properties of the thus obtained unvulcanized compositions and properties, resistance to heat ageing and compression set of the resulting vulcanization products were determined in the same manner as in Examples 1 to 6. Results of determination are given in the following Table 17.
TABLE 17
______________________________________
Comparative Examples
4 5 6 7 8 9
______________________________________
<Properties of unvulcanized
compositions>
Mooney viscosity (ML.sub.1+4, M)
56 41 49 54 38 48
Scorch time (min.)
17.4 19.6 15.0 18.1 8.6 8.3
<Vulcanization product
properties>
Normal state physical
properties
Hardness (JIS-A, pts)
67 59 66 66 58 65
100% Modulus (kg/cm.sup.2)
65 40 58 60 39 70
Breaking strength (kg/cm.sup.2)
144 139 143 144 109 123
Breaking elongation (%)
180 250 220 200 272 170
Resistance to heat ageing
Hardness change (%)
+8 +13 +12 +8 +5 +12
Modulus change (%)
-5 +17 +6 -4 -8 +14
Breaking strength change (%)
-8 -15 -2 -7 -8 0
Breaking elongation change
+6 -8 -5 +2 -10 +6
(%)
Compression set (%)
35 21 23 39 45 16
<Other influences of
unsaturated compounds>
Unpleasant odor
observed none none
Skin irritation
observed none none
Deterioration of mold
observed none none
releasability
______________________________________
As injection moldability judging from mold dirt by attachment of tailings, the following results are obtained:
TABLE 18 ______________________________________ Examples Attachment of tailings ______________________________________ Example 1 ◯ Example 4 Δ Example 5 ◯ Example 7 ◯ Example 13 ◯ Example 16 Δ Example 17 ◯ Example 19 ◯ Example 25 ◯ Example 28 Δ Example 29 ◯ Example 31 ◯ Example 37 ◯ Example 40 Δ Example 41 ◯ Example 43 ◯ Example 49 ◯ Example 52 Δ Example 53 ◯ Example 55 ◯ Comp. Ex. 9 X ______________________________________
Claims (10)
1. An acrylic rubber composition, which comprises a halogen-containing acrylic rubber, a vulcanizing agent and at least one unsaturated compound selected from the group consisting of (1) carboxylic acid vinyl esters, (2) alkyl vinyl ethers, (3 ) lower alkyl cyclohexenes or cyclohexenecarboxylic acid caprolactone esters and (4) unsaturated dicarboxylic acid dialkyl or dialkenyl diesters wherein the alkyl group or the alkenyl group has 1-10 carbon atoms,
wherein the halogen-containing acrylic rubber is comprised of a copolymer of alkyl acrylate, as a main component, or alkyl acrylate and alkoxyalkyl acrylate, as main components, copolymerized with about 0.1 to about 10% by weight of a cross-linking site, halogen-containing monomer, based on the copolymer and
wherein the vulcanizing agent is selected from the group consisting of an aliphatic acid alkali metal salt/sulfur, trithiocyanuric acid/aliphatic acid alkali metal salt and a diamine or diamine carbamate/dibasic lead phosphite.
2. An acrylic rubber composition according to claim 1, wherein the halogen-containing acrylic rubber is a halogen- and carboxyl group-containing acrylic rubber.
3. An acrylic rubber composition according to claim 1, wherein the carboxylic acid vinyl esters are unsaturated compounds represented by the general formula RCOOCH═CH2, where R is an alkyl group having 1 to 20 carbon atoms or an aryl group.
4. An acrylic rubber composition according to claim 1, wherein the alkyl vinyl ethers are unsaturated compounds represented by the general formula ROCH═CH2, where R is an alkyl group having 3 to 18 carbon atoms.
5. An acrylic rubber composition according to claim 1, wherein the lower alkyl cyclohexenes are cyclohexene derivatives, at least one of whose hydrogen atoms at 3-, 4-, 5- or 6-positions excluding the unsaturated bond is replaced with a lower alkyl group having 1 to 5 carbon atoms.
6. An acrylic rubber composition according to claim 1, wherein the lower alkyl cyclohexenes are cyclohexene derivatives, at least one of whose hydrogen atoms at 3-, 4-, 5- or 6-positions excluding the unsaturated bond is replaced with a lower alkyl group having 1 to 5 carbon atoms substituted by a lower alkoxy group having 1 to 5 carbon atoms.
7. An acrylic rubber composition according to claim 1, wherein the cyclohexenecarboxylic acid caprolactone esters are cyclohexene derivatives having a caprolactone ester group represented by the general formula --COO (CH2)5 COO!nCH2 R at the 3-position, where R is an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an alkoxyalkyl group or a cyclohexenyl group and n is an integer of 1 to 5.
8. An acrylic rubber composition according to claim 1, wherein the unsaturated dicarboxylic acid diesters are esters having two alkyl groups or two alkenyl groups, each group having 1 to 10 carbon atoms.
9. An acrylic rubber composition according to claim 1, wherein about 0.1 to about 30 parts by weight of the unsaturated compound is contained per 100 parts by weight of the halogen-containing acrylic rubber.
10. An acrylic rubber composition according to claim 1, wherein a plasticizer is further contained.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-120840 | 1995-04-21 | ||
| JP12084095A JP3601111B2 (en) | 1995-04-21 | 1995-04-21 | Acrylic rubber composition |
| JP7-125895 | 1995-04-26 | ||
| JP12589595A JP3538962B2 (en) | 1995-04-26 | 1995-04-26 | Acrylic rubber composition |
| JP7-125897 | 1995-04-26 | ||
| JP7-125896 | 1995-04-26 | ||
| JP12589895A JP3536424B2 (en) | 1995-04-26 | 1995-04-26 | Acrylic rubber composition |
| JP12589695A JP3538824B2 (en) | 1995-04-26 | 1995-04-26 | Acrylic rubber composition |
| JP7-125898 | 1995-04-26 | ||
| JP12589795A JP3591604B2 (en) | 1995-04-26 | 1995-04-26 | Acrylic rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5942580A true US5942580A (en) | 1999-08-24 |
Family
ID=27526893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/610,948 Expired - Lifetime US5942580A (en) | 1995-04-21 | 1996-03-05 | Acrylic rubber composition |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5942580A (en) |
| EP (1) | EP0738758B1 (en) |
| DE (1) | DE69612905T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263556A1 (en) * | 2003-09-15 | 2006-11-23 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
| US20060270783A1 (en) * | 2003-09-15 | 2006-11-30 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11279287A (en) | 1998-03-31 | 1999-10-12 | Nippon Shokubai Co Ltd | Water-absorption agent composition and its production |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264612A (en) * | 1987-04-22 | 1988-11-01 | Tosoh Corp | Acrylic copolymer elastomer |
| US4792581A (en) * | 1985-12-28 | 1988-12-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Rubber composition |
| JPH01123809A (en) * | 1987-11-10 | 1989-05-16 | Tosoh Corp | Acrylic copolymer elastomer |
| US4908400A (en) * | 1987-02-16 | 1990-03-13 | Du Pont-Showa Denko Co., Ltd. | Plasticizer for chloroprene rubber and plasticized chloroprene rubber |
| JPH0331351A (en) * | 1989-06-29 | 1991-02-12 | Tosoh Corp | Acrylic rubber composition |
| JPH04142356A (en) * | 1990-10-02 | 1992-05-15 | Tosoh Corp | Acrylic rubber composition |
| US5262479A (en) * | 1992-11-24 | 1993-11-16 | National Starch And Chemical Investment Holding Corporation | Plasticizer resisant hot melt pressure sensitive adhesive |
| US5300582A (en) * | 1992-06-04 | 1994-04-05 | Shell Oil Company | Coupled elastomeric block copolymers |
-
1996
- 1996-03-01 EP EP96103132A patent/EP0738758B1/en not_active Expired - Lifetime
- 1996-03-01 DE DE69612905T patent/DE69612905T2/en not_active Expired - Lifetime
- 1996-03-05 US US08/610,948 patent/US5942580A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4792581A (en) * | 1985-12-28 | 1988-12-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Rubber composition |
| US4908400A (en) * | 1987-02-16 | 1990-03-13 | Du Pont-Showa Denko Co., Ltd. | Plasticizer for chloroprene rubber and plasticized chloroprene rubber |
| JPS63264612A (en) * | 1987-04-22 | 1988-11-01 | Tosoh Corp | Acrylic copolymer elastomer |
| JPH01123809A (en) * | 1987-11-10 | 1989-05-16 | Tosoh Corp | Acrylic copolymer elastomer |
| JPH0331351A (en) * | 1989-06-29 | 1991-02-12 | Tosoh Corp | Acrylic rubber composition |
| JPH04142356A (en) * | 1990-10-02 | 1992-05-15 | Tosoh Corp | Acrylic rubber composition |
| US5300582A (en) * | 1992-06-04 | 1994-04-05 | Shell Oil Company | Coupled elastomeric block copolymers |
| US5262479A (en) * | 1992-11-24 | 1993-11-16 | National Starch And Chemical Investment Holding Corporation | Plasticizer resisant hot melt pressure sensitive adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263556A1 (en) * | 2003-09-15 | 2006-11-23 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
| US20060270783A1 (en) * | 2003-09-15 | 2006-11-30 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69612905T2 (en) | 2001-10-11 |
| EP0738758A2 (en) | 1996-10-23 |
| DE69612905D1 (en) | 2001-06-28 |
| EP0738758B1 (en) | 2001-05-23 |
| EP0738758A3 (en) | 1998-08-26 |
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